Oil-soluble oxygen-containing polymers



United States Patent 3,033,828 OIL-SOLUBLE OXYGEN-CONTAININ G POLYMERS Richard C. Nelson, 2260 Hillside Court, Walnut Creek, Calif. No Drawing. Filed Feb. 23, 1960, Ser. No. 10,061 6 Claims- (Cl. 260-775) This invention relates to new polymeric products. More particularly, it relates to a new class of oil-soluble polarcontaining polymeric compounds having a long linear hydrocarbon backbone chain which is particularly useful as detergents, wear inhibitors and stabilizers for liquid hydrocarbon compositions.

It is an object of the invention to provide a new class of polymeric compounds. It is a further object to provide a new oil-soluble polymeric compound having a long hydrocarbon backbone chain and a polar radical attached thereto through a methylene group. It is a further object to provide new polymers which are useful as detergents, and wear inhibitors for petroleum products such as lubricating oil and fuel compositions. These and other objects of the invention will be apparent from the following detailed description thereof.

It has now been discovered that these and other objects may be accomplished by the new and novel polymeric products of the invention which comprise oil-soluble polymeric compounds having essentially a long linear hydrocarbon backbone chain and attached thereto, in a uniform or random fashion, two essential groups, one being an oil-solubilizing oleophilic hydrocarbon radical, preferably an alkyl radical having an average of between 8 and 20 carbon atoms, preferably 10-18, bonded indirectly thereto through an oxygen-containing polar group such as an ester or an amide group, and the other being a polar-containing group CH -X, wherein X is a polar group such as hydroxy, carboxyl, cyano, sulfo, amine, amide or carbamyl, preferably a hydroxyl, an amine, an amide or a carbamyl group.

Oil-soluble polymers of this type are prepared by reacting an allyl compound, e.g., allyl alcohol, allyl ester, allyl amine or an allyl amide and a polymerizable ester or amide having an oleophilic radical such as a long alkyl radical of at least 8, preferably from 10 to 18 carbon atoms, such as C1040 alkyl esters of acrylic or methacrylic acids, vinyl esters of long-chain fatty acids having at least 8 carbon atoms, N-C1o gn alkyl acrylamides, and mixtures thereof. copolymers of allyl compounds and long-chain alkyl esters of acrylic acids, such as esters of methacrylic acid and C C, fatty acids, are preferred.

The mol ratio of the allyl compound to the oleophilic ester or amide can vary within relatively wide limits, e.g., from 1:1 to 15:1, preferably from :1 to :1, respectively, and the polymer may have suitable molecular weights of from about 1,500 to over one million, preferably between 10,000 and 100,000.

The copolymerization may be carried out in the presence of a suitable oxygen-yielding initiator, such as a suitable peroxide or azo compound and at temperatures varying from room temperature to about 150 C.

-The allyl compounds used to form the copolymers, inter alia, include allyl alcohol, methallyl alcohol, allyl acetate, allyl propionate, allyl butyrate methallyl acetate, allyl amine, N,N-diethyl allylamine, N-allyl aniline, allyl formamide, esters of allyl alcohol and a carbamic acid,

' e.g., allyl carbamate, methallyl carbamate, N,N-diethyl allyl carbamate, and mixtures thereof.

Polymerizable monomers containing oleophilic components containing an aliphatic hydrocarbon chain of at Patented May 8, 1962 least 8 carbon atoms which is not part of the main hydrocarbon polymer chain includes polymerizable esters, and/ or amides of unsaturated acids. Suitable esters include acrylic and alkacrylic esters of aliphatic alcohols of at least 8 carbon atoms, preferably of from 10 to 20 carbon atoms, and include, inter alia, decyl acrylate, lauryl acrylate, stearyl acrylate, eicosanyl acrylate, docosanyl acrylate, decyl methacrylate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, and the like, and mixtures thereof.

Other substances include the vinyl esters of long-chain carboxylic acids such as vinyl laurate, vinyl palmitate, vlnyl stearate, vinyl oleate and the like and mixtures thereof; long-chain esters of vinylene dicarboxylic acids such as methyl lauryl fumarate; and methyl stearyl maleate, N-long chain hydrocarbon substituted amides of unsaturated acids such as N-stearyl methacrylamide, N-lauryl methacrylamide, N-stearyl acrylamide and the like. These components can be employed alone or in various combinations. The technical lauryl methacrylate obtained from the commercial mixture of long-chain alcohols in the C to C range derived from coconut oil is an especially useful oleophilic component of the copolymer. The group of acrylic and alkacrylic esters of aliphatic alcohols of at least eight carbon atoms are, in general, well suited as the oleophilic component of the copolymer.

The copolymers of allyl or methallyl alcoholsv and esters of methacrylic acid and C1048 fatty acids, e.g., lauryl and/or stearyl methacrylate are preferred. Copolymers of this type can be prepared by polymerizing an ester of acrylic or methacrylic acid such as lauryl or stearyl methacrylate with an excess of allyl alcohol or by hydrolyzing copolymers of allyl esters, such as allyl acetate or propionate, and an ester of methacrylic acid such as lauryl methacrylate. The method of preparing copolymers by the latter process is to hydrolyze copolymers obtained by reacting an oleophilic-containing monomer, such as a long chain alkyl ester of an acrylic acid, e.g., lauryl or stearyl methacrylate with a large excess of an allyl ester such as allyl acetate or allyl propionate. At least preferably over of the allyl ester groups should be converted to free hydroxyl groups.

The following examples are given as representative embodiments of the invention.

Example I To 29.5 moles of allyl alcohol at 80-100" C. were added each hour for seven hours 2.744 moles of lauryl methacrylate and 0.00793 mole of alpha,alpha-azodi-isobutyronitrile. After eight hours polymerization, the unreacted monomers were removed by distillation, and the oil-soluble copolymer had a molecular weight of about 10,000.

Example I! 10 moles of allyl acetate and 1 mole of lauryl methacrylate were reacted in the presence of ditertiary butyl peroxide at 80-100 C. for 2 to 8 hours.

The copolymer was then mixed with a mixture of methanol and ethanol and sodium methacrylate so as to effect a conversion of the acetate group to hydroxyl groups. The sodium acetate formed was removed by washing with isopropanol-water mixture and the resulting oil-soluble copolymer had a molecular weight of about 50,000.

The following examples further illustrate polymeric additives used in compositions of the present invention.

Temp., Mole Ratio of Allyl Compound/Olso- Degree oi Mol. Example Catalyst C. phllic Monomer Hyd gol- Wt.

III benzoyl perioxide.-. 100 allyle a(llcohol (10)/stearyl methacry- 25,000

a IV --do 100 allyl alcohol (l5)/mixtu.re of lauryl and 30, 000

gteiaryl methacrylate (1) in ratio 01' v dltertbutyl peroxide. 115 allyl 31 mm ()]N-stearyl methacrylm, 000

am e. VI -do 115 allyl alcohol (10)/1sury1methacrylate 20,000 V11 dn 115 allyl acetate (10)]1auryl acrylate 90 ,000 VIII benmy1peroxide.--- 80 methallyl acetate (10)/stearyl aerylate. .90 10,000 IX. do 100 atlylamlne (10),lauryl methacrylamide. 15, 000 X- do 85 allyl alcohol (12)]vinyl stearate 10, 000 X1..- do 100 aliylecarbamate (10)]lauryl ""y- 000 Polymeric products of this invention are outstanding additives for various liquid hydrocarbon products, such as natural and synthetic hydrocarbon lubricating oils, greases, fuels (gasoline, gas oil, burner fuel oil), a'sphalts, waxes, slushing oils, industrial oils, e.g., metal working and drawing oil, quenching oils, textile oils, dielectric compositions and other industrial oils. They are particularly outstanding when added in small amounts to lubricating oils and lubricating compositions to impart detergency and anti-wear properties to such materials. Also, they are useful additives for gasoline, fuel oils and other light oil products.

The novel polymers are effective in liquid hydrocarbon compositions such as mineral lubricating oil compositions in ranges from about 0.001% to about 10%, preferably from about 0.02% to about 1% by weight. The lubricating stock for this purpose can be any natural or synthetic hydrocarbonaceous material having lubricating properties. Thus, the base may be a hydrocarbon oil of wide viscosity range, e.g., 100 SUS at 100 F. to 150 SUS at 210 F. The hydrocarbon oils may be blended with fixed oils such as castor oil, lard oil and the like, and/or with synthetic lubricants such as polymerized olefins, copolymers of alkylene glycols and oxides; organic esters of polybasic organic and inorganic acids, e.g., di-Z-ethylhexyl sebacate, dioctyl phthalate, trioctyl phosphate; polymeric tetrahydrofuran; polyalkyl silicone polymers, e.g., dimethyl silicone polymer and the like. In addition the base can be gasoline, fuel oils or greases.

In addition to the above-described lubricating oil compositions such composition can be modified with small amounts of other additives (0.01-2%) such as pour point depressants, viscosity index improyers, blooming agents, corrosion inhibitors, oiliness agents, solubilizer, and the like. Among such materials are-high-molecular-weight polymer, e.g., Acyloids, which are polymeric esters of methacrylic acid and long-chain fatty alcohols, e.g., mixtures of wax-naphthalene condensation products, isobutylene polymers, alkyl styrene polymers; inorganic and organic nitrites such as NaNO, and diisopropylammonium nitrite and dicyclohexylammonium nitrite; organic phosphites, phosphates and phospbonates such as trichloroethyl phosphite, tricresyl phosphate, dilorolphosphate, phosphorus sulfide-olefinic reaction products such as P s -terpene reaction products, metal organic phosphates, e.g., Ca or Zn dicyclohexylthiophosphate or Z-ethylhexylthiophosphate; organic sulfides, e.g., wax disulfide, ethylene bistolyl sulfide; amines, e.g., octadecylamine and the like. Also, phenolic antioxidants such as 2,6-diter,tiary- 4-methyl phenol, 2,6 ditertiary-4-methylol phenol, and 2,2'-methylene bis(4-methyl-o-tertiarybutylphenol) as well as conventional metallic detergents of the sulfonate and phenate class exemplified by alkali and alkaline earth organic sulfonates and phenates, e.g., Na, basic Ca or basic Ba petroleum sulfonate and Na, Ca, Ba, or Zn cetyl phenate, basic Ca or basic Ba C -C alkyl salicylate and Ca, Ba or Zn salt of octyl phenol-formaldehyde condensation product, etc., can be used in conjunction with the polymers of this invention.

To illustrate the manner in which the invention may be carried out, the following examples are given. It is to be understood, however, that the examples are for the purpose of illustration and the invention is not to be regarded as limited to any of the specific materials recited therein.

The improvement imparted to oils by polymers of this invention is shown by the following test results. To a mineral oil (150 SUS 210 F.) having an L1 engine rating for top ring groove filling of 100 (100=poor, 0=perfect) and an EX-3 engine cleanliness rating of 53 (100=perfect, 50=poor) was added 10% basic calcium petroleum sulfona-te and 0.75% zinc dihexyl dithiophosphate (composition X) and the EX-3 rating was increased to 65. However, when 1% of additive of Example I was added to composition X (composition A) the EX-3 rating was increased to 70. A mineral oil ('150 SUS 210 F.) containing 10% basic calcium petroleum sulfonate, 1.2% zinc dihexyldithiophosphate and 5% co polymer of lauryl methacrylate/2-methyl-5-vinyl pyridine (composition Y) gave an L-1 rating of however, when the vinyl pyridine copolymer in composition Y was replaced with 1% of additive of Example I (composition B) the L-l rating was reduced to 10. The L-l engine test is described in the CRC Handbook and the EX-3 engine test (6 cylinder) is essentially the same as described in SAE preprint 18, Detroit, Meeting Jan. 15-17, 1958.

When various amounts of from 0.1% to 10% of the polymeric material of Examples II to X are incorporated in various mineral oils such as SAE 10, 20, 30, low-30 and similarly tested as noted above, beneficial results are obtained as a result of the polymeric additives of this invention.

This application is a continuation-in-part of copending application Serial No. 742,505, filed June 17, 1958.

I claim as my invention:

1. An oil-soluble copolymer of (1) an allylic compound selected from the group consisting of an allyl alcohol, an allyl amine, and an allyl carbamate and (2) a polymcrizable ester selected from the group consisting of a C1048 alkyl acrylate and a vinyl carboxylate having from 10 to 18 carbon atoms in the molecule, in the mol ratio of 1) to (2) of from 1:1 to 15:1 respectively, the copolymer having a molecular weight of at least 1500.

2. An oil-soluble copolymer of allyl alcohol and a C -alkyl acrylate in the mol ratio of 1:1 to 15:1, respectively, and having a molecular weight of at least 1500.

3. An oil-soluble copolymer of allyl alcohol and lauryl methacrylate in the mol ratio of 1:1 to 15:1, respectively, and having a molecular weight of at least 1500.

4. An oil-soluble copolymer of allyl alcohol and lauryl methacrylate in the mol ratio of 5:1 to 10:1, respectively,

and having a molecular weight between 10,000 and 100,000.

5. An oil-so1uble copolymer of allyl carbamate and a C -alkyl methacrylate, in the mol ratio of 1:1 to 15: 1, respectively, and having a molecular weight of at least 1500.

6. An oil-soluble copolymer of allyl carbamate and Iauryl methacrylate, in the mol ratio of 15:1 to 1:1, respectively, and having a molecular weight of at least 1500.

References Cited in the file of this patent UNITED STATES PATENTS Bauer et a1. June 17, 1952 Neher et al June 17, 1952 Van Horne et a1. June 17, 1952 Van Horne et al. June 17, 1952 Stewart et a]. June 30, 1959 Lowe et al. June 30, 1959 Stewart et al. June 30, 1959 Lowe et al. June 30, 1959 

1. AN OIL-SOLUBLE COPOLYMER OF (1) AN ALLYLIC COMPOUND SELECTED FROM THE GROUP CONSISTING OF AN ALLYL ALCOHOL, AN ALLYL AMINE, AND AN ALLYL CARBAMATE AND (2) A POLYMERIZABLE ESTER SELECTED FROM THE GROUP CONSISTING OF A C10-18 ALKYL ACRYLATE AND A VINYL CARBOXYLATE HAVING FROM 10 TO 18 CARBON ATOMS IN THE MOLECULE, IN THE MOL RATIO OF (1) TO (2) OF FROM 1:1 TO 15:1 RESPECTIVELY, THE COPOLYMER HAVING A MOLECULAR WEIGHT OF AT LEAST
 1500. 